Copolymers of propylene with hexene-1 and blown films obtained from them

ABSTRACT

A copolymer of propylene with hexene-1 containing from 5 to 9% by weight of recurring units derived from hexene-1, having a melting temperature from 125 to 140° C. and Melt Flow Rate (ASTM D1238, 230/2.16 Kg) from 0.1 to 3 g/10 min., is used to produce blown films having valuable mechanical and optical properties.

This application is a Divisional Application that claims benefit to U.S.Non-Provisional application Ser. No. 12/735,148, filed Jun. 18, 2010,that is the U.S. National Phase of PCT International ApplicationPCT/EP2008/065907, filed Nov. 20, 2008, claiming the benefit of 35 USC119(e) 61/008,476, filed Dec. 20, 2007, claiming priority of EuropeanPatent Application No. 07150085.4, filed Dec. 18, 2007, the contents ofwhich are incorporated herein by reference in its entirety.

The present invention relates to copolymers of propylene with hexene-1,particularly suited for preparing blown films, and to the blown filmscomprising such copolymers.

The blown films sector constitutes an area of ever-increasing importancein various application segments, such as industry packaging, consumerpackaging, bags and sacks, lamination films, barrier films, packaging ofmedical products, agriculture films, hygienic products and productspackaging.

One of the reasons for this is that the films obtained by blowing have atubular shape which makes them particularly advantageous in theproduction of bags for a wide variety of uses (bags for urban refuse,bags used in the storage of industrial materials, for frozen foods,carrier bags, etc.) as the tubular structure enables the number ofwelding joints required for formation of the bag to be reduced whencompared with the use of flat films, with consequent simplification ofthe process. Moreover, the versatility of the blown-film technique makesit possible, simply by varying the air-insufflation parameters, toobtain tubular films of various sizes, therefore avoiding having to trimthe films down to the appropriate size as is necessary in the techniqueof extrusion through a flat head.

Blown film orientation, which is an essential parameter for mechanicalperformance, can be balanced between film extrusion and film crossdirections by the correct choice of processing parameters such asblow-up ratio, draw-down ratio, air cooling intensity and distributionand extrusion speed. This comes in combination with the use of lowfluidity materials to provide superior film mechanical performancecompared to the cast film process; in fact, cast films are based on highfluidity, low molecular weight thermoplastic resins and are usuallystrongly oriented in machine direction, which is the reason formechanical weakness such as easy tear propagation in the extrusiondirection.

In addition, blown films have homogeneous mechanical properties in crossdirection in contrast to cast films, the mechanical performance of whichis not constant over the web width due to melt distribution andtemperature variations resulting from film extrusion through a flat die.

The blown film gauge variation in transverse direction is easilydistributed and equalized with the help of reversing haul-off devices,which enables the production of perfectly cylindrical reels without theoccurrence of “piston rings”; on the other hand, in the case of the castfilm process, for instance, due to linear film movement resulting fromfilm extrusion making use of a flat die, gauge variations can not bedistributed on wide distances but only slightly shifted left and rightby a tiny transversal oscillation of the winding device, which may leadto reels of films with an imperfect shape.

Also in the case of cast films, good reel quality and acceptable filmproperties in the transverse direction can be achieved only by trimmingthe edge beads from the flat film; the edge trim material is eitherdiscarded or recycled, which comes at a cost, or re-fed into theextrusion process, which adds complexity to the cast film process andmay also generate quality problems due to multiple pass of thermoplasticresins through the extruder. In addition, edge trim refeeding is morecomplicated in the case of multi-layered films due to the choice of thefilm layer in which the edge trim material must be added. In the case ofmultilayered barrier films which contain one or more non-polyolefinicresin such a polyamide, EVOH or so called tie layer material, edge trimis usually discarded since it can not be refed or recycled due toquality considerations, which is an additional cost burden related tothe cast film process. On the other hand, blown films exhibit constantproperties and film thickness in transverse direction and therefore donot require edge trimming, which saves cost, material and avoidstechnical complications such as edge trim refeeding and associatedquality issues.

The most common thermoplastic resins used in the production of blownfilms belong to the polyethylene family of products, such as LDPE,LLDPE, MDPE or HDPE, or mixtures therefrom, since these polyethyleneresins are endowed with properties in the molten state which enablesfilms to be obtained with a high level of production efficiency and in avery wide range of thicknesses, without compromising the stability ofthe bubble. However by using polyethylene materials it is still notpossible to achieve a fully satisfactory balance of high stiffness, highclarity, good mechanical properties and high thermal resistance. Thus itwould be desirable to produce blown films made of or comprising polymermaterials capable of providing the said balance to a higher level. Inparticular, polypropylene would be an ideal candidate, because it isknown to provide improved stiffness and yield strength, even attemperatures above room temperature.

The use of polypropylene-based polymers in blown films, on the otherhand, is particularly difficult given the poor processability propertiesof polypropylene which give rise to frequent tearing of the bubble,requiring reduction of the process throughput, or, in any case, toexcessive orientation of the film, resulting in an impact resistance anda resistance to tear propagation in the machine direction which are solow as to render it unusable. Useful solutions are proposed in WO9720888and WO97020889, wherein blown films prepared from complex blends aredisclosed.

However the films disclosed in the said documents are not yet fullysatisfactory because the throughput achievable on blown film lines isnot yet at the level which can be obtained with polyethylene resins. Inaddition, comparatively good mechanical performance is achieved by theincorporation of high level of soft modifier resins which lower the filmstiffness required for downgauging and material saving in downstreamapplications and uses, also impairing the thermal film stabilitycompared to the non-modified polypropylene-based film. It is alsorequired to carry out complex blending operations.

It is therefore seen that there is a need for a polyolefin materialwhich at the same time is of good processability on blown-filmproduction lines under high throughput conditions and is capable ofproviding films with valuable mechanical properties together with goodstiffness and thermal resistance.

Now it has surprisingly been found that a good balance of mechanicalproperties, in particular of impact resistance (e.g. dart drop impactstrength) and resistance to tear propagation, can be obtained in blownfilms made from new specific copolymers of propylene with hexene-1. Dueto the relatively low amounts of hexene-1, such copolymers also maintainthe resistance to thermal deformation which is typical for propylenepolymers. Moreover, the said films show good optical properties, inparticular haze and gloss, and are easily obtainable by processing thecopolymers of the present invention in the existing blown film lines.

Thus the present invention provides a copolymer of propylene withhexene-1 containing from 5 to 9% by weight, preferably from 5.5 to 9% byweight, more preferably from 6 to 9% by weight, in particular from 6.5to 9% by weight, of recurring units derived from hexene-1, saidcopolymer having a melting temperature from 125° C. to 140° C.,preferably from 128° C. to 139° C., and Melt Flow Rate (MFR, measuredaccording to ASTM D 1238, 230° C./2.16 kg, i.e. at 230° C., with a loadof 2.16 kg) from 0.1 to 3 g/10 min.

The said amounts of hexene-1 units are referred to the total weight ofthe copolymer. The said melting temperature values are determined bydifferential scanning calorimetry, according to ISO 11357-3, with aheating rate of 20° C./minute.

Recurring units derived from other comonomers, selected in particularfrom ethylene and CH₂═CHR α-olefins where R is a C₂-C₈ alkyl radical,hexene-1 excluded, can be present, provided that the final properties ofthe copolymer are not substantially worsened. Examples of the saidCH₂═CHR α-olefins are butene-1, 4-methyl-1-pentene, octene-1. Among thesaid other comonomers, ethylene is preferred.

Indicatively, the total amount of recurring units derived fromcomonomer(s) different from propylene and hexene-1 in the copolymer ofthe present invention is from 0.5 to 2% by weight, referred to the totalweight of the copolymer.

From the above definition, it is evident that the term “copolymer”includes polymers containing more than one kind of comonomers, such asterpolymers.

Moreover, the copolymer of the present invention is semicrystalline, asit has a crystalline melting point, and typically has a stereoregularityof isotactic type.

Preferably, said copolymer exhibits at least one of the followingfeatures:

-   -   A solubility in xylene at room temperature (i.e. about 25° C.)        equal to or lower than 25% by weight, preferably equal to or        lower than 20% by weight.    -   Isotacticity Index equal to or higher than 97%, determined as m        diads/total diads using ¹³C-NMR;    -   A molecular weight distribution expressed by the Mw/Mn ratio,        measured by GPC, (Gel Permeation Chromathograpy), from 4 to 7.

It has been found that the above said combination of Melt Flow Rate andmelting temperature, characterizing the copolymers of the presentinvention, can be obtained with polymerization processes carried out inthe presence of stereospecific Ziegler-Natta catalysts supported onmagnesium dihalides. By properly dosing the molecular weight regulator(preferably hydrogen), the said combination of Melt Flow Rate values andcorresponding melting temperature values is achieved, when the amount ofrecurring units derived from hexene-1 is within the above said range offrom 5 to 9% by weight.

The polymerization process, which can be continuous or batch, is carriedout following known techniques and operating in liquid phase, in thepresence or not of inert diluent, or in gas phase, or by mixedliquid-gas techniques. It is preferable to carry out the polymerizationin gas phase.

Polymerization reaction time, pressure and temperature are not critical,however it is best if the temperature is from 20 to 100° C. The pressurecan be atmospheric or higher. As previously mentioned, the regulation ofthe molecular weight is carried out by using known regulators, hydrogenin particular.

The said stereospecific polymerization catalysts comprise the product ofthe reaction between:

-   1) a solid component, containing a titanium compound and an    electron-donor compound (internal donor) supported on magnesium    dihalide (preferably chloride);-   2) an aluminum alkyl compound (cocatalyst); and, optionally,-   3) an electron-donor compound (external donor).

Said catalysts are preferably capable of producing homopolymers ofpropylene having an isotactic index higher than 90% (measured as weightamount of the fraction insoluble in xylene at room temperature).

The solid catalyst component (1) contains as electron-donor a compoundgenerally selected among the ethers, ketones, lactones, compoundscontaining N, P and/or S atoms, and mono- and dicarboxylic acid esters.

Catalysts having the above mentioned characteristics are well known inthe patent literature; particularly advantageous are the catalystsdescribed in U.S. Pat. No. 4,399,054 and European patent 45977.

Particularly suited among the said electron-donor compounds are phthalicacid esters and succinic acid esters.

Suitable succinic acid esters are represented by the formula (I):

wherein the radicals R₁ and R₂ equal to or different from each other,are a C1-C20 linear or branched alkyl, alkenyl, cycloalkyl, aryl,arylalkyl or alkylaryl group, optionally containing heteroatoms; theradicals R₃ to R₆ equal to or different from each other, are hydrogen ora C1-C20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkylor alkylaryl group, optionally containing heteroatoms, and the radicalsR₃ to R₆ which are joined to the same carbon atom can be linked togetherto form a cycle.

R₁ and R₂ are preferably C1-C8 alkyl, cycloalkyl, aryl, arylalkyl andalkylaryl groups. Particularly preferred are the compounds in which R₁and R₂ are selected from primary alkyls and in particular branchedprimary alkyls. Examples of suitable R₁ and R₂ groups are methyl, ethyl,n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Particularlypreferred are ethyl, isobutyl, and neopentyl.

One of the preferred groups of compounds described by the formula (I) isthat in which R₃ to R₅ are hydrogen and R₆ is a branched alkyl,cycloalkyl, aryl, arylalkyl and alkylaryl radical having from 3 to 10carbon atoms. Another preferred group of compounds within those offormula (I) is that in which at least two radicals from R₃ to R₆ aredifferent from hydrogen and are selected from C1-C20 linear or branchedalkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group,optionally containing heteroatoms. Particularly preferred are thecompounds in which the two radicals different from hydrogen are linkedto the same carbon atom. Furthermore, also the compounds in which atleast two radicals different from hydrogen are linked to differentcarbon atoms, that is R₃ and R₅ or R₄ and R₆ are particularly preferred.Other electron-donors particularly suited are the 1,3-diethers, asillustrated in published European patent applications EP-A-361 493 and728769.

As cocatalysts (2), one preferably uses the trialkyl aluminum compounds,such as Al-triethyl, Al-triisobutyl and Al-tri-n-butyl.

The electron-donor compounds (3) that can be used as externalelectron-donors (added to the Al-alkyl compound) comprise the aromaticacid esters (such as alkylic benzoates), heterocyclic compounds (such asthe 2,2,6,6-tetramethylpiperidine and the 2,6-diisopropylpiperidine),and in particular silicon compounds containing at least one Si—OR bond(where R is a hydrocarbon radical). Examples of the said siliconcompounds are those of formula R_(a) ¹R_(b) ²Si(OR³)_(c), where a and bare integer numbers from 0 to 2, c is an integer from 1 to 3 and the sum(a+b+c) is 4; R¹, R², and R³ are alkyl, cycloalkyl or aryl radicals with1-18 carbon atoms optionally containing heteroatoms.

Thexyltrimethoxysilane (2,3-dimethyl-2-trimethoxysilyl-butane) isparticularly preferred.

The previously said 1,3-diethers are also suitable to be used asexternal donors. In the case that the internal donor is one of the said1,3-diethers, the external donor can be omitted.

The catalysts may be precontacted with small quantities of olefin(prepolymerization), maintaining the catalyst in supension in ahydrocarbon solvent, and polymerizing at temperatures from room to 60°C., thus producing a quantity of polymer from 0.5 to 3 times the weightof the catalyst.

The operation can also take place in liquid monomer, producing, in thiscase, a quantity of polymer up to 1000 times the weight of the catalyst.

The copolymer of the present invention can also contain additivescommonly used for olefin polymers like, for example, nucleating andclarifying agents and processing aids.

Suitable clarifying agents include the acetals of sorbitols and xylitolsas well as phosphate ester salts. Many such clarifying agents aredisclosed in U.S. Pat. No. 5,310,950. Specific examples of acetals ofsorbitols include dibenzylidenesorbitol or its C₁-C₈-alkyl-substitutedderivatives such as methyldibenzylidenesorbitol,ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol. Examples ofsuitable commercially available sorbitol-acetal clarifying agents arethose designated as Millad 3940 and Millad 3988, both available fromMilliken Chemical. Specific examples of phosphate ester salts include2,2′-methylenebis (4,6,-di-tert-butylphenyl)phosphate sodium or lithiumsalt. Examples of commercially available phosphate ester salts for useas clarifying agents include ADK stabilizer NA-71 and ADK StabilizerNA-21, both available from Amfine Chemical Corp. Particularly preferredclarifying agents are 3,4-dimethyldibenzylidenesorbitol;aluminum-hydroxy-bis[2,2′-methylene-bis(4,6-di-t-butylpheny)phosphate];sodium 2,2′-methylene-bis(4,6-ditertbutylphenyl)phosphate and otherclarifying agents different from sorbitols and phosphate ester saltssuch as N,N′,N″-tris-isopentyl-1,3,5-benzene-tricarboxoamide,bicyclo[2.2.1]heptane-2,3-dicarboxylic acid disodium or calcium salt(1R,2R,3R,4S) or the commercial nucleating agent NJ Star PC1.Combinations of any of the above may also be employed.

The clarifying agent may be added to the copolymer of the presentinvention by known methods, such as by melt blending the clarifyingagent and the copolymer under shear condition in a conventionalextruder.

Preferred amounts of clarifying that can be added to the copolymer ofthe present invention are up to 2500 ppm, more preferably from 100 to2000 ppm by weight (with respect to the total weigh of the copolymer andthe clarifying agent).

Particular examples of processing aids are fluoropolymers, such asDynamar FX5911, sold by 3M, and other equivalent polymer materials knownin the art.

As previously said, the present invention provides also a blown filmcomprising the said copolymer of propylene with hexene-1 containing from5 to 9% by weight of recurring units derived from hexene-1, saidcopolymer having a melting temperature from 125° C. to 140° C.,preferably from 128° C. to 139° C., and Melt Flow Rate (ASTM D1238, 230°C./2.16 Kg) from 0.1 to 3 g/10 min.

The blown film may be prepared by the processes and with the relatedequipment generally used in the technique of blown films.

The technique of blown film (also referred to as the Tubular Film)extrusion is well known for the production of thin plastic films. Theprocess involves extrusion of a molten thermoplastic resin through acircular die, followed by “bubble-like” expansion of the molten web.

Standard practice favors single-screw extruders with barrel diameters of25 to 200 mm for melting thermoplastic resins and homogeneously meltingand delivering the molten polymer to the die head. Two different type offeed sections, either smooth or grooved, are commonly used.

Conventional extruders with a smooth feed are sometimes encountered onblown film line, but have a narrow operating range for screw speed andoutput. Usually the output achieved with a die of given flow resistancedoes not increase in proportion to an increase in screw speed. With aconstant screw speed, the output decreases with increasing dieresistance. The melt temperature becomes disproportionately high withincreasing pressure and screw speed. The barrel heaters are set so thatthe barrel wall temperature increases in the direction of flow. The bulkof the energy required for plastification is imparted to the melt byshear forces, i.e. by converting the mechanical drive energy into heat.The conveying behavior of conventional extruders is dependent on thetemperature of the extruder barrel, as the temperature influences thefriction conditions in the extruder. In order for the melt to beconveyed, the friction between the plastic and the barrel must begreater than that between the plastic and the screw. The conveyingcapacity of the screw is largely governed by the pressure in front ofthe screw tip. This pressure, in turn, is dependent on the flow rate,the die resistance, the extrusion temperature and the flowcharacteristics of the melt. For this reason, the geometry of the diemust be brought into line with that of the screw.

For the most part, blown film lines are manufactured with a grooved feedsection. The friction is governed predominantly by the geometry of thebarrel wall. In order to maintain a high conveying rate, the groovedsection must be intensively cooled. The design of the extruder barrelmust ensure good thermal isolation between the cooled grooved sectionand the heated barrel. The raw material properties that determine theconveying rate are density, coefficient of friction and pellet form.

The different conveying mechanisms in extruders with grooved and withsmooth feed sections necessitate different screw geometries. Forexample, the flight depth in the feed section of an extruder with asmooth feed section must be considerably larger than in an extruder witha grooved feed section. In both systems, the screws generally have abarrier zone.

The use of shear and mixing sections is recommended for practically allscrew geometries on extruders with grooved feed sections. Shear sectionsensure in particular the residual plastification. Thanks to the highshear stresses in the narrow melt channels, they also contribute tobreaking down filler agglomerations and colouring pigments. The mostwidespread are spiral shear sections and Maddock shear sections.

In contrast to the shear sections, the main function of the mixingsections is melt distribution. Their homogenizing effect derives fromthe intensive mixing of the melt. Apart from the established pin type,slotted disc and transverse bore mixing sections, mixing sections inwhich cavities are machined into the inner wall of the extruder barreland into the screw, are also suitable for the processing ofthermoplastic resins.

Extruders allow blown film line outputs of between 5 and 1500 kg/h.Almost all machine manufacturers today provide equipment with a screwlength of 30 times the screw diameter (30D) as standard for single-screwextruders. Melt filters hold back impurities carried into the extruderwith the plastic pellets and prevent the die from becoming blocked ordamaged. Melt filters are therefore particularly important whenprocessing regrind and non-virgin material. The installation of a screenchanging device is advisable. Manual or semiautomatic changing devicesare generally sufficient.

The screen pack in the melt filter allows the pressure in front of thescrew tip to be influenced. In many cases, a selective pressureadaptation improves the homogenizing effect of the screw. Only screensof stainless steel should be used. Screens of brass or copper can resultin catalysis, causing cross-linking of thermoplastic resins such aspolyethylene.

Blown film lines are equipped with at least one and with up to ninedifferent extruders feeding a die assembly. Coextrusion systems formaking multilayer films employ at least two extruders feeding a commondie assembly. The number of extruders is dependent upon the number ofdifferent materials comprising the coextruded film. For each differentmaterial, a different extruder is advantageously used. Thus a five-layercoextrusion may require up to five extruders although less may be usedif two or more of the layers are made of the same material. The term“coextrusion” refers here to the process of extruding two or morematerials through a single die with two or more orifices arranged suchthat the extrudates merge together into a laminar structure, preferablybefore chilling or quenching.

In the blown film process, the molten polymer feeding the die assemblyis forced through an annular die. Air is introduced via a hole in thecentre of the die to blow up the tube like a balloon. The bubble that isformed is hauled-off at a higher speed than the die outlet speed. It isintensively cooled by a current of air so that the temperature at thefrost line is lower than the crystallite melting point. The bubbledimensions are fixed here. The bubble is then collapsed, trimmed ifnecessary, and rolled-up using a suitable winding system.

In modern tubular film plants, the common extrusion direction isvertical upwards. When producing smaller film formats, machines arestill used in which the film bubble is extruded downwards. The filmsproduced by these processes have gauges ranging from 8 to 250 μm. Spiralmandrel dies with vertical orientation of the spirals are almostexclusively used for the production of single-layer blown films. Thedies generally have a ring diameter of between 50 and 2000 mm. The gapdie width normally lies between 0.8 and 2.5 mm. The choice of gap widthis primarily dependent on the thermoplastic resin to be extruded. Therheologically correct design of the die is a major determining factorfor the uniformity of the film gauge.

For many years, the production of multi-layer blown films was onlypossible using dies in which the individual melt streams were passedthrough concentrically arranged spiral dies with vertical orientation ofthe spiral channels which are then joining only just before the dieexit.

It is now more conventional to use “stack” dies, which consist of anumber of stacked plates—one for each melt stream—each containing aspiral flow channel. The individual melt streams are merged together insuccession. Some stack dies allow separate temperature control of eachplate. The long flow path of the merged melt streams can prove adisadvantage in some cases.

Most machine manufacturers today offer both stack dies and multi-layerdies. Multilayer dies are generally used for film with up to threelayers. Stack dies are more commonly used for films with five and morelayers.

Uniform cooling around the circumference of the film bubble is animportant precondition for ensuring the bubble has minimal diameter andgauge fluctuations. One or more air cooling rings are used for coolingdown the molten bubble emerging from the die below the crystallizationline which forms in the bubble. The air current generated by a fan isguided by the cooling ring at a defined speed along the outer surface ofthe bubble. The volume, velocity and temperature of the cooling airdetermine the geometry of the film bubble in the bubble expansion zone.

Uniform film production at increased throughput demands cooling air witha constant temperature. For this reason, ambient air is not recommendedfor cooling. Chilled air, on the other hand, allows uniform and constantproduction conditions. In addition, it increases the cooling capacityand hence the output of a blown film line. It should be noted, however,that air temperature below 10° C. can cause humidity in the air tocondense on the surface of the cooling ring. This then impairs theproduction process.

Most efficient single cooling rings are dual lipped. With this coolingring type, air arrives at the film bubble via two outlet gaps. Thisimproves the bubble stability, in particular during the processing ofthermoplastic resins with low melt viscosity, which can thus beprocessed with a comparatively high output through the use of twin lipcooling rings.

Cooling air rings can also be used in combination to cool down the blownfilm bubble at different positions between the die lips and thecrystallization line. In a modern configuration, two air rings are usedin combination. The lower air ring is conventionally fixed to the die,whereas the upper cooling ring can be moved up and down to facilitateline start up operations but also precise adjustment of the position andintensity of the air flow reaching the external bubble surface.

Almost all modern blown film extrusion lines allow the air inside thefilm bubble to be exchanged. This so-called internal bubble cooling(IBC) increases the cooling capacity and contributes to stabilizing thefilm bubble, therefore enhancing throughput capability of the blown filmprocess. In order to ensure a well-controlled exchange of air inside thefilm bubble, the bubble diameter is continuously monitored usingultrasonic sensors or mechanically sensing arms.

The design of the cooling facility has a significant influence on theform of the film bubble. Typically, the expansion ratio between die andblown tube of film would be 1.5 to 5 times the die diameter. Thedrawdown between the melt wall thickness and the cooled film thicknessoccurs in both radial and longitudinal directions and is easilycontrolled by changing the volume of air inside the bubble and byaltering the haul off speed. This gives blown film a better balance ofproperties than traditional cast or extruded film which is drawn downalong the extrusion direction only.

The tube of film then continues upwards, continually cooling, until itpasses through nip rolls where the tube is flattened to create what isknown as a ‘lay-flat’ tube of film.

Between the frost line and collapsing frames, the inflated film bubblepasses through a calibrating basket which stabilizes the film bubble andprovokes disturbance in the cooling air flow, thus enhancing thermalexchange between cooling air and film surface. Height and diameter ofthe calibrating basket can generally be varied according to bubble sizeand stability requirements. It is common for the adjustable guide armsof the basket to be fitted with small PTFE rollers.

Apart from the gauge tolerance, the flatness is one of the mostimportant quality criteria for blown film. For this reason, blown filmextrusion lines must be equipped with a suitable collapsing and haul-offdevice. Collapsing devices with wooden slatted boards are common, but onmodern equipment the collapsing boards are equipped with self-rotatingbrush systems, aluminum or carbon fiber rollers. It is very common forthe bubble collapsing angle and the position of the lateral triangles tobe controlled by motors. This technique enables the machine operator toadjust the collapsing device quickly at size changes from a remotecontrol panel. These adjustment facilities enable drag and side creasesto be avoided.

The collapsing boards are positioned immediately before the mainhaul-off system, which is made of two mechanically driven, rotatingcalendars which are pressing the collapsed bubble into a flat tubing.Rubber-coated squeeze rolls have proven to be effective for the filmhaul-off. In many cases, only one of the two haul-off rolls is rubbercoated. The second roll serves as a chill roll and helps to increase theoutput of the film line. This lay-flat or collapsed tube is then takenback down the extrusion tower via more rollers.

Even modern machine engineering cannot prevent film bubbles exhibitingslight deviations in gauge in transverse direction. To prevent thick andthin area from developing in the film roll during winding and causingthe formation of “piston rings”, machine manufacturers have nowdeveloped devices which shift differences in film gauge backwards andforwards during winding, permitting the formation of cylindrical filmreels without deformations.

In reversing haul-off devices, the reversing bars can be arrangedhorizontally or vertically. The benefit of vertical systems is thecomparatively simple construction and the price. Horizontal systemsoffer technical benefits, particularly with very wide and very thinfilm, but are more expensive. In the meantime reversing bar systems havemore or less completely superseded systems in which the film die or thewhole extruder platform rotates.

The lay-flat film is then either kept as such or the edges of thelay-flat are slit off to produce two flat film sheets and wound up ontoreels. If kept as lay-flat, the tube of film can be made into bags,liners or covers by sealing across the width of film and cutting to makeeach bag, liner or cover. This is done either in line with the blownfilm process or at a later stage. Final cutting to size of the film isperformed directly in front of the winder. The slitting unit can takethe form of replaceable industrial blades or as circular blades (shearslitting) in conjunction with a grooved roll. An adjustable transversestretching roll is generally installed in the inlet section of theslitting unit which ensures crease-free running. With blown films,slitting knives are frequently used to cut the flat tubing into two filmwebs without loss and without edge trimming using internal spreading andslitting devices.

When winding film, the winding characteristics must be adapted to thespecific properties of the film such as friction behavior, rigidity,etc.

In order to produce relatively hard reels such as desired, the windingtension (i.e. the tension in the film) must remain constant when thereel diameter increases. The drive torque must therefore increase withthe winding diameter.

A distinction is made between three winder types according to theirbasic design, namely contact winders, center winders and gap winders. Incase of contact winders, an independently driven pressure roll ispressed against the reel surface and thus sets the winding reel inrotation. The winder shaft itself is normally not driven. Torque andspeed of the pressure roll remain constant during the whole windingprocess. In case of the centre winder technique, the winder shaft isdriven. Consequently the torque and speed must change during the windingprocess so that winding tension and haul-off speed remain constant. Thegap winder is a combination of contact winder and centre winder, whereaspressure roll and reel do not contact one another; the gap between rolland reel is held constant during the winding process and the pressureroll and the winder shaft are driven separately. The combination of allthe methods in one winder is also possible.

Modern high-performance winders are designed so that any of these threewinding methods can be set. A dedicated DC motor with tension andcharacteristic control drives each winding point. Furthermore, suchwinders are equipped with a fully automatic reel changing system whichalso includes the cutting and laying-on of the film web. Reversing ofthe direction of rotation of the winding shafts allows the position ofthe two film sides (e.g. in case of surface pre-treatment) to beinverted. Thanks to their modular design, the winders can be employedeither as single-station winders for flat tubing or as tandem windersfor slitted, flat films.

The principal benefits of manufacturing film by the blown film processinclude the ability to produce tubing (both flat and gussetted) in asingle operation, to regulate film width and thickness by control of thevolume of air in the bubble, the output of the extruder and the speed ofthe haul-off, to eliminate end effects such as edge bead trim andnon-uniform temperature that can result from flat die film extrusion, toobtain biaxial orientation (allowing uniformity of mechanicalproperties), and to manufacture co-extruded, multi-layer films for highbarrier applications such as food packaging.

Thus the present invention provides also a blown film process, whereinthe copolymer of propylene with hexene-1 of the present invention isused to produce at least one layer of the film.

In the said process it is preferable to operate according to thefollowing main settings and conditions:

The extrusion is preferably performed with grooved feed bore extrudersand with a modern screw with a dual-flight barrier element. Still morepreferably, the extrusion screw is equipped with at least one additionalmixing element.

The screw length is preferably from 20 to 40 times the screw diameter,more preferably from 25 to 35 times the screw diameter. Most preferably,the screw length is from 27 to 33 times the screw diameter.

The barrel and die temperatures are generally from 160 to 270° C.

In particular, the extruder barrel temperature settings are preferablyfrom 160 to 270° C., more preferably from 180 to 260° C., in particularfrom 200 to 250° C.

The melt temperature which is obtained with these temperature settingsis preferably from 210 to 260° C., which can be in excess of thetemperature settings due to the possibility of self-heating of themolten polymer under shearing stress conditions.

The die temperature is preferably from 200 to 270° C., more preferablyfrom 210 to 250° C., in particular from 220 to 240° C.

Film extrusion is preferably performed in vertical upward direction.

The blow-up ratio is preferably from 2.2 to 4, more preferably from 2.4to 3.6.

The die diameter can be any commercial die dimension, from 30 mm to 2 mor higher; preferably, the die diameter is from 100 mm to 1 m, morepreferably from 150 mm to 650 mm.

Film cooling is performed with cooling fluids, which can be either in aliquid or in a gaseous state. In case of cooling with a liquid coolingmedium, water is the preferred cooling medium, and the extrusiondirection is preferably vertical downward. In case of cooling with agaseous cooling medium, air is the preferred cooling medium, althoughother gases, such as nitrogen, can also be used, and the extrusiondirection is preferably vertical upward.

In case of gaseous film quenching, the cooling is preferably done withat least one dual lip cooling ring, although a single lip cooling ringcan also be used. Still preferably, internal bubble cooling (IBC) isused. The cooling medium temperature is preferably from 5 to 20° C.,more preferably from 10 to 20° C., most preferably from 8 to 15° C.

Optionally, air cooling is performed with two cooling air rings, wherethe lower air ring (in case of vertical upward film extrusion) isnon-movable in vertical direction and the position of the upper air ringcan be moved in vertical direction, in order to allow further throughputincrease in comparison with a single air ring cooling system.

The gap of the die ring (annular die gap) is preferably equal to or lessthan 3 mm, more preferably equal to or less than 1.8 mm, in particularfrom 0.6 to 3 or from 0.6 to 1.8 mm, most preferably from 0.8 to 1.8 mm.

Typical blown film applications include industry packaging (e.g. shrinkfilm, stretch film, stretch hoods, bag film or container liners),consumer packaging (e.g. packaging film for frozen products, shrink filmfor transport packaging, food wrap film, packaging bags, or form, filland seal packaging film), laminating film (e.g. laminating of aluminiumor paper used for packaging for example milk or coffee), barrier film(e.g. film made of raw materials such as polyamides and EVOH acting asan aroma or oxygen barrier, used for packaging food, e. g. cold meatsand cheese), films for the packaging of medical products, agriculturalfilm (e.g. greenhouse film, crop forcing film, silage film, silagestretch film).

The thickness of the film of the present invention is generally below250 μm, preferably below 150 μm. It can be a monolayer or multilayerfilm.

In the multilayer films, at least one layer comprises the copolymer ofthe present invention. It is preferable that at least the base layer(also called “support layer”) comprise the copolymers of the presentinvention. The other layer(s) may comprise other kinds of polymers.

Examples of olefin polymers that can be used for the other layers arepolymers or copolymers, and their mixtures, of CH₂═CHR olefins where Ris a hydrogen atom or a C₁-C₈ alkyl radical.

Particularly preferred are the following polymers:

-   a) isotactic or mainly isotactic propylene homopolymers, and    homopolymers or copolymers of ethylene, like HDPE, LDPE, LLDPE;-   b) Semi-crystalline copolymers of propylene with ethylene and/or    C₄-C₁₀ α-olefins, such as for example butene-1, hexene-1,    4-methyl-1-pentene, octene-1, wherein the total comonomer content    ranges from 0.05% to 20% by weight with respect to the weight of the    copolymer, or mixtures of said copolymers with isotactic or mainly    isotactic propylene homopolymers;-   c) elastomeric copolymers of ethylene with propylene and/or a C₄-C₁₀    α-olefin, optionally containing minor quantities (in particular,    from 1% to 10% by weight) of a diene, such as butadiene,    1,4-hexadiene, 1,5-hexadiene, ethylidene-1-norbornene;-   d) heterophasic copolymers comprising a propylene homopolymer and/or    one of the copolymers of item b), and an elastomeric fraction    comprising one or more of the copolymers of item c), typically    prepared according to known methods by mixing the components in the    molten state, or by sequential polymerization, and generally    containing the said elastomeric fraction in quantities from 5% to    90% by weight;-   e) butene-1 homopolymers or copolymers with ethylene and/or other    α-olefins.

Examples of polymers different from polyolefins, employable for theother layers, are polystyrenes, polyvynylchlorides, polyamides,polyesters and polycarbonates, copolymers of ethylene and vinyl alcohol(EVOH) and “tie layer” resins.

Finally, the films of the present invention can undergo a series ofsubsequent operations, such as:

surface embossing, by heating the surface and compressing it against anembossing roller;

printing, after having made the surface ink sensitive through oxidating(for instance flame) or ionizing treatments (for instance coronadischarge treatment);

coupling with fabric or film, particularly of polypropylene, by heatingof the surfaces and compression;

coextrusion with other polymeric or metallic materials (e.g. aluminumfilm);

plating treatments (depositing a layer of aluminum through evaporationunder vacuum, for example);

application of an adhesive layer on one of the two faces of the film,thus producing an adhesive film.

Depending upon the specific kind of film and final treatment, the filmof the present invention can find many uses, the most important of whichis goods and food packaging.

The following examples are given to illustrate the present inventionwithout limiting purpose.

The data relating to the polymeric materials and the films of theexamples are determined by way of the methods reported below.

Melting Temperature (ISO 11357-3)

Determined by differential scanning calorimetry (DSC). A sampleweighting 6±1 mg, is heated to 200±1° C. at a rate of 20° C./min andkept at 200±1° C. for 2 minutes in nitrogen stream and it is thereaftercooled at a rate of 20° C./min to 40±2° C., thereby kept at thistemperature for 2 min to crystallise the sample. Then, the sample isagain fused at a temperature rise rate of 20° C./min up to 200° C.±1.The melting scan is recorded, a thermogram is obtained, and, from this,temperatures corresponding to peaks are read. The temperaturecorresponding to the most intense melting peak recorded during thesecond fusion is taken as the melting temperature.

Melt Flow Rate (MFR)

Determined according to ASTM D 1238, at 230° C., with a load of 2.16 kg.

Solubility in Xylene

2.5 g of polymer and 250 ml of xylene are introduced in a glass flaskequipped with a refrigerator and a magnetical stirrer. The temperatureis raised in 30 minutes up to the boiling pint of the solvent. The soobtained clear solution is then kept under reflux and stirring forfurther 30 minutes. The closed flask is then kept for 30 minutes in abath of ice and water and in thermostatic water bath at 25° C. for 30minutes as well. The so formed solid is filtered on quick filteringpaper. 100 ml of the filtered liquid is poured in a previously weighedaluminium container, which is heated on a heating plate under nitrogenflow, to remove the solvent by evaporation. The container is then kepton an oven at 80° C. under vacuum until constant weight is obtained. Theweight percentage of polymer soluble in xylene at room temperature isthen calculated.

Intrinsic Viscosity (IV)

Determined in tetrahydronaphthalene at 135° C.

1-Hexene Content and Isotacticity

Determined by ¹³C-NMR spectroscopy.

¹³C-NMR spectra are acquired on a Bruker DPX-600 spectrometer operatingat 150.91 MHz in the Fourier transform mode at 120° C.

The samples are dissolved in 1,1,2,2-tetrachloroethane-d2 at 120° C.with a 8% wt/v concentration. Each spectrum is acquired with a 90°pulse, 15 seconds of delay between pulses and CPD (WALTZ 16) to remove¹H-¹³C coupling. About 1500 transients are stored in 32K data pointsusing a spectral window of 6000 Hz.

The peak of the Propylene CH is used as internal reference at 28.83 ppm.

The evaluation of diad distribution and the composition is obtained fromSαα a using the following equations:PP=100Sαα(PP)/ΣPH=100Sαα(PH)/ΣHH=100Sαα(HH)/ΣWhereΣ=ΣSαα[P]=PP+0.5PH[H]=HH+0.5PHM _(w) and M _(n)

Measured by way of Gel Permeation Chromatography (GPC), preferablycarried out in 1,2,4-trichlorobenzene; in detail, the samples areprepared at a concentration of 70 mg/50 ml of stabilized 1,2,4trichlorobenzene (250 μg/ml BHT (CAS REGISTRY NUMBER 128-37-0)); thesamples are then heated to 170° C. for 2.5 hours to solubilize; themeasurements are run on a Waters GPCV2000 at 145° C. at a flow rate of1.0 ml/min. using the same stabilized solvent; three Polymer Lab columnsare used in series (Plgel, 20 μm mixed ALS, 300×7.5 mm).

Elmendorf Tear Strength

Determined according to ASTM D 1922 both in the machine direction (MD)and in the transverse direction (TD).

Puncture Resistance and Deformation

Determined from the energy required to puncture the film with a plunger(50 mm, diameter of 4 mm) with a rate of 20 mm/min, followed bymeasuring the deformation.

Haze

Determined according to ASTM Method D 1003.

Clarity

Determined according to ASTM D 1746.

Gloss at 45°

Determined according to ASTM D 2457.

Dart Test

Determined according to ASTM method D 1709A.

Tensile Modulus

Determined according to ASTM D882, both in the machine direction (MD)and in the transverse direction (TD).

Stress and Elongation at Yield and at Break

Determined according to ASTM D 882, both in the machine direction (MD)and in the transverse direction (TD).

Preparation of the Copolymer of Propylene with Hexene-1

The copolymer is prepared as follows.

The solid catalyst component used in polymerization is a highlystereospecific Ziegler-Natta catalyst component supported on magnesiumchloride, containing about 2.2% by weight of titanium anddiisobutylphthalate as internal donor, prepared by analogy with themethod described in WO03/054035 for the preparation of catalystcomponent A.

Catalyst System and Prepolymerization Treatment

Before introducing it into the polymerization reactor, the solidcatalyst component described above is contacted at 15° C. for about 6minutes with aluminum triethyl (TEAL) and thexyltrimethoxysilane(2,3-dimethyl-2-trimethoxysilyl-butane), in aTEAL/thexyltrimethoxysilane weight ratio equal to about 7 and in suchquantity that the TEAL/solid catalyst component weight ratio be equal toabout 6.

The catalyst system is then subjected to prepolymerization bymaintaining it in suspension in liquid propylene at 20° C. for about 20minutes before introducing it into the polymerization reactor.

Polymerization

The polymerization is carried out in a gas phase polymerization reactorby feeding in a continuous and constant flow the prepolymerized catalystsystem, hydrogen (used as molecular weight regulator), propylene andhexene-1 in the gas state.

The main polymerization conditions are:

-   -   Temperature: 75° C.    -   Pressure: 1.6 MPa;    -   molar ratio H₂/C3−: 0.0005;    -   molar ratio C6−/(C6−+C3−): 0.0453;    -   residence time: 96 minutes.

Note: C3−=propylene; C6−=hexene-1.

A polymer yield of 8400 g of polymer/g of solid catalyst component isobtained.

The polymer particles exiting the reactor are subjected to a steamtreatment to remove the reactive monomers and volatile substances, andthen dried.

The resulting propylene copolymer contains 7.3% by weight of hexene-1.Moreover said propylene copolymer has the following properties:

-   -   MFR: 0.3 g/10 min.;    -   Amount of fraction soluble in xylene: 18.1% by weight;    -   Melting temperature: 132.3° C.

Before using it to prepare films, the said copolymer of propylene withhexene-1 is extruded with additives, thus obtaining the copolymermaterials COPO-1 and COPO-2.

COPO-1 is obtained by extruding the said copolymer with 500 ppm byweight of Dynamar FX5911.

COPO-2 is obtained by extruding the said copolymer with 500 ppm byweight of Dynamar FX5911 and 1800 ppm by weight of Millad 3988.

Dynamar™ FX5911 is a fluoropolymer sold by 3M for use as processing aid.

Millad 3988 is a clarifying agent based onbis(3,4-dimethyldibenzylidene) sorbitol.

Examples 1 and 2 and Comparison Examples 1 to 4

Three layer films are prepared on a Collin three layer coextrusion line.The film of Example 1 is prepared by using COPO-1 for all the threelayers. The film of Example 2 is prepared by using COPO-2 for all thethree layers.

In Comparison Example 1 the polymer material used for the all the threelayers is a copolymer of propylene with butene-1 containing 15% byweight of butene-1 and having a MFR value of 0.8 g/10 min., previouslyextruded with 500 ppm by weight of Dynamar FX5911.

In Comparison Example 2 the same copolymer of propylene with butene-1 asin Comparison Example 1 is used for all the three layers, but previouslyextruded with 500 ppm by weight of Dynamar FX5911 and 1800 ppm by weightof Millad 3988.

In comparison Example 3 the polymer material used for all the threelayers is copolymer of propylene with ethylene containing 5% by weightof ethylene and having a MFR value of 2 g/10 min., previously extrudedwith 1800 ppm by weight of Millad 3988.

In comparison Example 4 the polymer material used for all the threelayers is a copolymer of propylene with ethylene containing 6.5% byweight of ethylene and having a MFR value of 2.3 g/10 min., previouslyextruded with 500 ppm by weight of Dynamar FX5911 and 1800 ppm by weightof Millad 3988.

All the said extrusions with Dynamar FX5911 and Millad 3988 are carriedout in a co-rotating twin screw three lobs profile extruder (ZSK53 type,length/diameter ratio of 20, manufactured by Coperion Werner&Pfleiderer)under nitrogen atmosphere in the following conditions:

Rotation speed: 220 rpm;

Extruder output: 80 kg/hour;

Melt temperature: 250-260° C.

In the said Collin coextrusion line, the screw length/screw diameterratios are 30 mm/30 xD for extruders A & C while 45 mm/30 xD for the Bone. No IBCS system (Internal Bubble Cooling System) is used. During theextrusion trials, the melt is extruded through an annular die with adiameter of 100 mm and a quite narrow gap (0.8 mm for the trials). Atthe exit from the die, the melt tube is subjected to intensive aircooling, immediately blown up to about three times the diameter of thedie and stretched in the direction of the flow.

The main operating conditions in Examples 1 and 2 are:

-   -   Barrel temperature: 200-240-220-220-220° C.;    -   Adaptor temperature: 220° C.;    -   Die temperature: 230-250-230-225-230° C.;    -   Screw speed: 30 rpm for all the three extruders;    -   Blow-up ratio: 3.1;    -   Line speed: 5.3 m/min.

In Comparison Examples 1 and 2 the same conditions as in Examples 1 and2 are used, except for the following:

-   -   Screw speed: 50 rpm for all the three extruders;    -   Blow-up ratio: 3;    -   Line speed: 10 m/min.

In Comparison Examples 3 and 4 the same conditions as in Examples 1 and2 are used, except for the following:

-   -   Barrel temperature: 200-240-220-210-210° C.;    -   Adaptor temperature: 210° C.;    -   Die temperature: 240-250-240-250-250° C. in Comparison Example 3        and 230-245-230-230-230° C. in Comparison Example 4;    -   Blow-up ratio: 2.8 in Comparison Example 3 and 2.9 in Comparison        Example 4;    -   Line speed: 7 m/min.

The final film thickness of the films is approximately 50 micron, with athickness distribution (in percentage) of 20/60/20.

The properties of the so obtained films are reported in Table 1.

TABLE 1 EXAMPLE No. 1 2 Comp. 1 Comp. 2 Comp. 3 Comp. 4 Elmendorf (MD)g/μm 1.3 1.1 0.5 0.4 0.2 0.3 Elmendorf (TD) g/μm 1.8 1.7 1.1 0.8 0.3 0.4Puncture N 9.7 12.8 7.2 11.1 9.5 7.5 resistance Puncture mm 10.3 13.79.3 13.3 12.3 14.3 deformation Haze % 8.7 4.2 9.0 6.6 7.4 4.0 Clarity %96.1 98.1 88.3 87.4 95.0 92.5 Gloss at 45° ‰ 63.5 80.0 63.0 69.8 63.875.1 Dart test g/μm 11.33 7.47 2.27 1.43 1.32 1.54 Tensile MPa 329 511587 575 638 480 Modulus (MD) Tensile MPa 321 518 606 645 671 515 Modulus(TD) Stress at MPa 14.1 24.8 22.0 21.5 23.1 18.8 yield (MD) Stress atMPa 14.2 23.0 20.3 20.8 22.2 18.5 yield (TD) Elongation at % 14.9 15.913.1 12.5 15.1 16.0 yield (MD) Elongation at % 14.8 15.1 12.5 11.7 13.815.0 yield (TD) Stress at MPa 38.1 42.0 36.9 43.5 31.0 37.6 break (MD)Stress at MPa 38.9 34.0 28.5 41.9 30.0 32.9 break (TD) Elongation at %668 670 700 850 870 1000 break (MD) Elongation at % 718 626 710 990 9701000 break (TD) Note: Comp. = Comparison

What is claimed is:
 1. A blown film comprising: a layer consistingessentially of a copolymer of propylene and hexene-1, wherein the layercomprises from about 5 to about 9% by weight of recurring units derivedfrom hexene-1 based upon the total amount of propylene and hexene-1,wherein the copolymer has a melting temperature from 125° C. to 140° C.,a molecular weight distribution from 4 to 7, and Melt Flow Rate (ASTMD1238, 230° C./2.16 kg) from 0.1 to 3 g/10 min.
 2. The blown film ofclaim 1, wherein the blown film has a thickness of less than about 250μm.
 3. The blown film of claim 1, wherein the copolymer has a solubilityin xylene at room temperature of less than or equal to 25% by weight. 4.The blown film of claim 1, wherein the copolymer further comprises aclarifying agent.
 5. The blown film of claim 1, wherein the copolymerwas formed by polymerizing the propylene and hexene-1 in the presence ofa stereospecific Ziegler-Natta catalyst comprising a solid componentcomprising a titanium compound and an electron-donor compound supportedon magnesium chloride, an aluminum alkyl compound and an externalelectron-donor compound.
 6. The blown film of claim 5, wherein theexternal electron-donor compound is selected from silicon compoundscomprising at least one Si—OR bond, where R is a hydrocarbon radical. 7.The blown film of claim 6, wherein the external electron-donor compoundis thexyltrimethoxysilane.
 8. The blown film of claim 1, wherein theblown film is processed into an article comprising the blown film,wherein the article is selected from the group consisting of anindustrial package, a food package, a bag, a sack, a lamination film, abarrier film, an agriculture film, and a hygienic product.
 9. The blownfilm of claim 1, wherein the blown film is blow molded into a film layercomprising at least the blown film.
 10. The blown film of claim 9,wherein the blow molding process is carried out under the followingconditions: (i) screw length from 20 to 40 times the screw diameter;(ii) barrel and die temperatures from 160 to 270° C.; (iii) annular diegap equal to or less than 3 mm; (iv) blow-up ratio from 2.2 to 4; and(v) cooling medium temperature from 5 to 20° C.